Splitting up of tars, crude mineral oils, and the like



Oct. 5 1926.

1,602,310 M. MELAMID SPLITTING UP OF TARS CRUDE MINERAL OILS, AND THE LIKE Filed July 5. 1923 INVENYTOR.

I /7- 777e/ami BY W2C2Q A TTORNEYS.

Patented Oct. 5, 1926.

' UNITED STATES 1,602,310 PATENT OFFICE.

MICHAEL MELAMID, OF FREIBURG, GERMANY.

SPLITTING UP OF TABS, CRUDE MINERAL OILS, AND THE LIKE.

Application filed July 5, 1923, Serial No.

This invention refers broadly to a process for the splitting up of mineral oils, tar oils, 1nd the like and of the substances from which they are usually obtained, such as 5 crude tars, crude kerosene and raw naphtha and the like, and it'is intended to generally improve the methods of producing light hydrocarbons from such substances in the presence of metals. In a revious application, Serial No. 510,082, ed Oct. 24., 1921, I have described arprocess for the manufacture of hydrocarbons of comparatively low boiling points from tar oil s, mineral 'oils and the like. In further pursuance of the principles outlined I have ascertained that not only distillation products and fractions from tars, petroleum-products and the like are subject to this kind of decomposition, but that rawmaterials of this kind, even where they occur as waste products may still be employed with advantage for obtaining such decomposition products. In connection with this procedure it has been found that unforeseen favorable economical 2 and industrial results are accomplished by the fact that in the working of this process the raw materials may be completely converted and without leaving a residue, such as pitch, cokes,asphaltum and the like, very valuable hydrocarbon fluids of low boilin points and lubricating oils being obtaine in this manner. The conversion is effected in such a manner that the hydrocarbons both of the saturated and unsaturated parafline series as well as of the aromatic series are formed in continuous homologous series up to the highest boiling substances capable of economical and industrial application. I

The process may also be carried out, with the richest carboniferous material of this kind. that is to say with coal or carbon it self, in an easy and industrially economical manner. It is an essential condition for the success- 43 ful carrying out of the process on an industrial scale that the raw material is finely distributed and in .this condition is brought into intimate contact with a catalyzer, preferably such catalyzers as will be liquid at the temperature of reaction, and in particular a liquid metal. This metal, however, should not be such, as to easily form carbides, and in view thereof the use of lead will be entirely excluded as well as the use of zinc, only tin, antimony and bismuth and alloys of the same being known to come up 649,689, and in Germany April 28, 1923.

Thus, for example, small stillsmay be employed which are charged with the contact material in liquid or solid condition according to the nature and composition of said contact material, but at all events in such a manner as to present an extended contactin surface to the mixture of raw material an protecting gas or fluid. In ,these kinds of apparatus which should be more or less highly heated in accordance with the nature of the substance-and the decomposition desired the substance to be decomposed is injec'ted by blowing and by the aid of a protecting gas, such as hydrogen. The injection should be effected in such a manner that an exceedingly fine spray or a fo of the substance to be treated is produced. The

spraying and disintegration may be produced in different ways, such for instance, by means of spraying nozzles, by pressure pumps, constructed for example in the mannerof the fuel pumps employed for the Diesel engine, and by all equivalent or similar methods which produce a reliable disintegration.

The products of reaction may be collected separately and may be united according to requirements, and may, if desired, be submitted to a fresh treatment until the, desired final productsare obtained.

The efliciency and output of the apparatus may be considerably increased byarranging a plurality of reaction vessels in parallel connection, and then effecting the union of the more or less decomposed substances only in the additional reaction chambers, the

vaporous or gaseous products finally obtained being then submitted to a normal condensing process with or without the usual preliminary. separating apparatus. By the term protective gas I mean every gas mixture which is adapted to avoid dehydrogenation. .In accordance with my previous observations it is preferable to use a protective gas containing hydrogen. I may also make use as a protective gas of the hydrocarbon vapors produced in the course of reaction- It has also been found that by the new process hereinbefore outlined I am not only enabled to produce the decomposition an conversion of tar products, oil products and the like which have been sprayed and disintegrated and converted into a fogby protective gases or hydrogen, but that the gaseous and fog-like tar products discharged from gas chambers, producers, and the like may be directly submitted to the treatment. 'In such cases the gases generated in the gasifiers, producers, carburettors or the like in which coal, carbon, wood and equivalent substances are decomposed into gas, tar and ashes contain hydrogen with other indifl'ercut or inert protective gases, and it is therefore not necessary to add hydrogen, but it is sufiicient to introduce the mixture, as soon asit is formed, into the reaction chambers.

The gas produced furnishes the hydrogen for the chemical process, and the remaining gas serves as a protecting or diluting agent. The mixture of fogs of gas and tar in exceedingly fine dispersion is then introduced into the reaction chambers by a pump or fan, located in front or between the reaction chambers or behind the same, or in any other suitable manner and is caused to pass through the reaction material and through the reaction chambers. The separation of the oily and benzine-like constituents distributed in the gas'is then effected in the well known manner by cooling, washing, compression and the like. The remaining permanent gases separated off from the condensing constituents are conducted away for any usual or other utilization. It is necessary, of course, to exclude as much as possible the presence of oxygen.

Examples ofemecutz'on of the process.

1. Producer tar from lignite, mixed coals, or other coal is heated until it is well liquefied and is introduced into the apparatus by means of nozzles or pressure pumps together with the mechanical impurities and in the presence of protective gas, a liquid alloy being contained in the apparatus. In the few moments of the engagement of the fog-like mixture with the contact material at a high temperature the first part of the reaction takes place. The mixture is then submitted to a further similar treatment in additional similar pieces of apparatus arranged in series with the reaction chambers first mentioned, and the number of which is governed by the degree of decomposition to which it is desired to submit the material. Olefinic, parafline-lilce and aromatic hydrocarbons are thereby produced and gas which may be Well known methods.

separated from the hydrocarbon therein by The bodies containing oxygen and soluble in sodium hydrate are either converted into more stable phenols and cresols or they are decomposed into hydrocarbons or lower boiling oxygen containing fractions, such as acetone and the like. The nitrogen containing bodies are either converted into hydrocarbons and ammonia or they are converted into basic bodies of different nature, but adapted for industrial utilization in the arts. Inasmuch as the procedure is continuous, it will be unnecessary to mention percentages of the output obtained, but it should be pointed out that, for instance, lower boiling hydrocarbons are formed to the amount of from 30 to 4-0 per cent, and that of the portions soluble in alkali lye about one half thereof on an average are converted into hydrocarbons and phenols of high value and cresol at the first stage of the procedure.v Pitch and pitch-like portions and cokcs are not formed, but a certain amount of hydrogenated hydrocarbons are formed which upon repeating the procedure may be converted into low boiling hydrocarbons of the kind first mentioned.

2. Crude oils containing 45 to 50% of asphaltum residues with sulphur are sprayed in the same manner'or disintegrated by blowing and, are introduced into the correspondingly heated reaction masses, and in the case of petroleum at temperatures, for instance of about 500 degrees centigrade. According to the amount of thesubstance to be treated the reaction chambers are arranged in parallel connection in the first stage, and in series connection with the following reaction chambers and stages, the

several pieces of apparatusv being then united in the last stage'of condensing vessels. Similar to the procedure in the distillation of crude oils the different fractions are obtained, and in such a manner that no pitch-like or asphaltic masses are produced, the easily boiling. fractions amounting upwards to about 50 'per cent of the raw material according to the operating procedure: or the residual products belong to the series of light oils and lubricating oils, and may be further split in accordance with industrial and economic requirements, and may be decomposed into the standard trade products. In case parafiines, lignite tars or the like should be present in some of these substances, this parafline may be separated or may be decomposed into low boiling hydrocarbons; but at any rate the separated fractions obtained, when the parafiine is separated. are of particularly highavaluc, be cause the paraflines are obtained in very large crystals, and in this manner may be easily separated off even from the oils which are present in the coal tar and mineral oil products and the like.

On the accompanying drawing I have shown diagrammatically and by way of exemplification only, and without limiting the invention thereto, a combination of pieces of apparatus for carrying out the invention in plan view. "In the drawing]. indicates a pump, blower or the like connected'to the source of material to be treated. 2, 3, 4 and respectively 2, 3, 4' are indicative of two parallelly disposed sets of treating chambers, towers, scrubbers or the like containing the catalyst and sultably connected to the pump or the like 1 and also connected to each other. At the end of these two or more series of treating units the mixture of materials or the reaction products may be delivered by means of a fan or the like 5 into a number of treating units 6, 7 in series connection and which are succeeded by condensers, washers or the like 8, 9.

The chimney is indicated at 10. It is obvious that I am not restricted to any particular number of units, and may employ more or less of them according to varying requirements, and their relative position and the position of the pressure and suction producing means is entirely immaterial for the purposes of my invention. The pressure and temperature employed are governed by the nature of the starting material and of the final products it is desired to obtain. Various other changes and modifications are possible within the meaning of the claims hereunto appended and without deviating from the spirit of my invention.

I claim:

1.. The process of treating tars, crude mmeral oils and similar substances and of preventing the separation of carbon and pitchymatter in the catalytic decomposition thereof, which consists in treating these substances at a high'temperature and in finely distributed condition, and in the presence" of a pro-' tective gaseous agent exclusively with a metal catalyzer in a substantially pure, me-

tallic condition and incapable of forming carbides.

2. The process of treating tars, crude mineral oils and similar substances and of preventing the separationof carbon and pitchy matter in the catalytic decomposition thereof, which consists in treating such material at a high temperatureand' in finely divided condition exclusively with a metal catalyzer in a substantially pure, metallic condition and incapable of forming carbides, andin the presence of a hydrogen-containing gaseous atmosphere.

3. The process of treating tars, crude mineral oils and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decomposition thereof, which consists in highly dispersing such material into fog-like condition, and treating it exclusively with a metal catalyzer in a sub stantially pure, metallic condition and liquefying at the temperature of reaction and inexclusively with a metal catalyzer in a substantially pure, metallic condition and incapable of forming;- carbides, and liquefying at the reaction temperature.

5. The process of treating tars, crude mineral oils and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decom osition thereof, which consists in highly ispersing such material into a fog, gas-like condition, mixing the, same with hydrogen, and treating the mixture exclusively with a metal catalyzer in a substantially pure, metallic condition and incapable of forming carbides, and liquefying at the reaction temperature in separate, simultaneous stages, then uniting the resulting reaction products and then repeating the treatment in consecutive stages.

6. The process of treating tars, crude mineral oils and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decomposition thereof, which consists in highly dispersing such material in the presence of a protective gas, preventing oxidation and carbonization, and

converting said material into a gas-like fog gy condition, and treating the product obtamed exclusively with a metal catalyzer in a substantially pure, metallic condition and liquefying at the reaction temperature, and

incapable of the formation of carbides, and 1 condensing and separating the reaction prodnets.

7. The process of treating tars, crude mineral oils and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decompositionthereof, which consists in highly dispersing such material in the presence of hydrogen, and thereby converting said material into a foggy, gas-like condition, and treating the mix- 1* ture obtained at a high temperature exclusively with a metal catalyzer in a substantially pure, metallic condition and liquefying at the temperature of reaction, and incapable of the formation of carbides.

8. The process of treating tars, crude mineral o ls and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decomposition thereof, which consists in treating the mixture of highly dispersed nebulized, tar-carrying byproducts from producers, gas chambers, carburettors and the like in the presence of hydrogen in finely dispersed condition exclusively with a metal catalyzer in a substantially pure, metallic condition and liquid at the reaction temperature and incapable of forming carbides, and separating solidifiable and condensable constituents from the prodnets of reaction.

9. The process of treating tars, crude mineral oils and similar substances and of preventing the separation of carbon and pitchy matter in the catalytic decomposition thereof, which consists in treating the mixture of gen, and exclusively with a metal catalyzer 15 in the substantially pure, metallic condition and liquid at the reaction temperature, and incapable of the formation of carbides.

MICHAEL MELAMID. 

